Method for producing polymeric polyamines

ABSTRACT

Polymeric polyamine is produced by polymerizing polyoxyalkylene-amine and a linker. The polyoxyalkylene-amine has a structural formula H 2 N—R—NH 2 , wherein R is selected from the group consisting of dianhydride, diacid, epoxy, diisocyanate and poly(styrene-co-maleic anhydride) copolymers (SMA). The linker can be anhydride, carboxylic acid, epoxy, isocyanate or poly(styrene-co-maleic anhydride) copolymers (SMA). The polymeric polyamine so produced can be used as a stabilizer or dispersant of the Ag nanoparticles.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a division of prior U.S. application Ser. No.13/195,022 filed Aug. 1, 2011, entitled “POLYMERIC POLYAMINES AND METHODFOR PRODUCING THE SAME” and currently pending. The prior U.S.application is a division of prior U.S. application Ser. No. 12/140,507filed Jun. 17, 2008, entitled “POLYMERIC POLYAMINES AND METHOD FORSTABILIZING SILVER NANOPARTICLE BY EMPLOYING THE SAME”, which has issuedas U.S. Pat. No. 8,013,048 on Sep. 6, 2011. The prior U.S. applicationsclaim priority of Taiwan Patent Application No. 096146929, filed on Dec.7, 2007, the entirety of which is incorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to polymeric polyamines and a method forstabilizing Ag nanoparticles by employing the same. The produced Agnanoparticles are in the form of silver slurry, silver gel or solid, andsuitable for composite material or antimicrobial material. Fields of thepresent invention include electric industries, for example, conductivesilver nanowires, parts and sensors, and biomedicine or medicinalindustries. In addition, the Ag nanoparticles have both hydrophilic andhydrophobic properties and therefore can be dissolved in water andorganic solvents, and are compatible with many kinds of polymers.Therefore, the product of the present invention is a good polymericsurfactant or dispersant suitable for dispersing nanoscale particles,for example, pigments and silver particles.

2. Related Prior Arts

The application of Ag nanoparticles is one of the most importanttechnologies in this century. The traditional methods for producingwater solutions of Ag nanoparticles are primarily to reduce silvernitrate or other silver salts with organic surfactants, dispersants orstabilizers for stabilizing the Ag nanoparticles. To exhibit goodeffects in antimicrobial, pharmaceutical, biomedicine and electricalapplications, the Ag particles have to keep in the nanoscale and largesurface areas without aggregation. Therefore, it's very important tocontrol size of the Ag particles in the nanoscale and maintain thermalstability thereof.

In processes for producing Ag nanoparticles, organic surfactants orstabilizers are an important operation factor. In addition, most silverslats, for example, silver nitrate, is more easily dissolved in waterthan organic solutions, and therefore the product is usually prepared inwater solution. That is, the existing conditions will restrictapplications of the Ag nanoparticles.

The above problems have been discussed in some reports. In J. Phys.Chem. B 1998, 102, 10663-10666, the Ag particles are prepared in watersolution and stabilized with molecular chains of sodium polyacrylate orpolyacrylamide. In Chem. Mater. 2005, 17, 4630-4635, thioalkylatedpoly(ethylene glycol) is used as a stabilizer for stabilizing Agparticles in water. In Langmuir 1999, 15, 948-951,3-aminopropyltrimethoxysilane (APS) is used as a stabilizer andN,N-dimethylformamide is used to reduce silver ions in water. In J.Phys. Chem. B 1999, 103, 9533-9539, sodium citrate is used to preventthe Ag particles from aggregation or agglomeration which results inlarger particle size, wider size distribution or multiple-peakdistribution. In Langmuir 1996, 12, 3585-3589, some nonionic surfactants(polyethylene oxide or ethoxylated block) are used to stabilize Agnanoparticles which are in the form of gel-type particles covered withmolecular chains of the surfactant, the examples includepoly-(10)-oxyethylene oleyl ether and Tween 80(polyoxyethylene-(20)-sorbitan monooleate) (available from Sigma). InLangmuir 1997, 13, 1481-1485, NaBH₄ is used as a reducing agent, and thereaction equation is:

2AgNO₃+2NaBH₄+6H₂O→2Ag+2NaNO₃+2H₃BO₃+7H₂

In this reaction, the stabilizers are cetyltrimethylammonium bromide(CTAB) as a cationic surfactant, sodium dodecyl sulfate (SDS) as ananionic surfactant and poly(oxyethylene)isooctylphenyl ether-TX-100 as anonionic surfactant.

As described in the above, the traditional method for stabilizing Agparticles is to add surfactants or stabilizers. However, the solutionsof such Ag particles have solid contents less than 10% and can not be inthe form of silver slurry, or have a higher solid content withaggregation.

SUMMARY OF THE INVENTION

The object of the present invention is to provide a polymeric polyamineand a method for producing the same, wherein polymeric polyamine can beapplied to producing Ag nanoparticles for stabilizing and dispersing.

Another object of the present invention is to provide a method forstabilizing Ag nanoparticles with polymeric polyamine, so that theproduced silver slurry, silver gel or solid silver has a high solidcontent and good stability, even after processing treatment orpreservation.

To achieve the above objects, polymeric polyamine of the presentinvention includes polyoxyalkylene-amine and a linker linking with anamino end thereof. The polyoxyalkylene-amine is preferably monoamine,diamine or triamine having a molecular weight about 200˜10,000, and thelinker can be anhydride, carboxylic acid, epoxy, isocyanate orpoly(styrene-co-maleic anhydride) copolymers (polystyrene-maleicanhydride polymers, SMA).

The proper linker includes: (1) anhydride, for example, maleicanhydride, succinic acid anhydride, trimellitic anhydride (TMA), benzenetetracarboxylic dianhydride (PMDA), phthalic anhydride,tetrahydromethyl-1,3-isobenzofurandione and poly(styrene-co-maleicanhydride) copolymers; (2) carboxylic acid, for example, dicarboxylicacid, adipic acid, succinic acid, p-phthalic, isophthalic acid; (3)glycidyl or epoxide, for example, diglycidyl ether of bisphenol-A(DGEBA), 3,4-epoxycyclohexyl-methyl-3,4-epoxy cyclohexane carboxylate;(4) isocyanate or diisocyanate, for example, toluene diisocyanate,methylen-biphenyldiisocyanate, 1,6-cyclohexamethylene-diisocyanate,methyl isopropyl ketone diisocyanate; and (5) maleic anhydride ormaleated polystyrene, for example, SMA. The preferred linker includesbenzene tetracarboxylic dianhydride (PMDA), trimellitic anhydride (TMA)and adipic acid.

The polymeric polyamine can have a structural formula:Linker-HN—R—NH-Linker, H₂N—R—NH-Linker, H₂N—R—NH-Linker,H₂N—R—NH-Linker-NH—R—NH₂, Linker-(HN—R—NH-Linker)x orH₂N—R—NH-(Linker-HN—R—NH)x-H; wherein x=1˜5, H₂N—R—NH and HN—R—NH arepolyoxyalkylene-amine, R can be dianhydride, diacid, epoxy, diisocyanateor poly(styrene-co-maleic anhydride) copolymers (SMA).

The method for producing polymeric polyamine is to reactpolyoxyalkylene-amine with a linker having a reactive functional group.Segments of polymeric polyamine may chelate silver nanoparticles, anddisperse in both water phase and an organic solvent. Accordingly, the Agnanoparticles can be prepared as a stable concentrated gel, slurry orpowders having a concentration more than 10 wt %. Thepolyoxyalkylene-amine and the linker are defined as the above.

For the process, molar ratio of the polyamine to the linker can bechanged to synthesize Linker-(HN—R—NH-Linker)x orH₂N—R—NH-(Linker-HN—R—NH)x-H, having different end functional groups.

After reaction of polyoxyalkylene-amine and the linker, the linkerprovides additional functional groups to enhance stability of silver inwater or the organic solvent by chelating with silver. The solution willbe more stable and the nanoparticles will not aggregate together.

The molar ratio of the linker to polyoxyalkylene-amine is preferably(n+1):n, n=1˜5, the reaction temperature is preferably about 25˜150° C.,and the reaction time is preferably about 1˜12 hours.

In the present invention, the method for stabilizing Ag nanoparticleswith polymeric polyamine includes steps of: (a) mixing polymericpolyamine and a water solution of silver salt; (b) reducing the Ag⁺ ionswith a reducer to form a solution of Ag nanoparticles. The polymericpolyamine serves as a stabilizer or a dispersant and comprisespolyoxyalkylene-amine and a linker linking with an amino end ofpolyoxyalkylene-amine.

The polyoxyalkylene-amine has a molecular weight about 200˜10,000, andthe linker is selected from the group consisting of anhydride,carboxylic acid, glycidyl, epoxide, isocyanate, diisocyanate, maleicanhydride and maleated polystyrene.

The reducer can be NaBH₄, methanol, ethanol, glycerin, ethylene glycol,dodecanol, H₂N—NH₂, formaldehyde, PVA or DMF. The weight ratio ofpolymeric polyamine to the silver salt is preferably about 1:10˜10:1.The silver salt can be AgNO₃, AgI, AgBr, AgCl or silverpentafluoropropionate.

The solution of Ag nanoparticles can be further dewatered to increasesolid content thereof. An organic solvent can be also added to transferthe particles into the organic solvent.

The solution of Ag nanoparticles can further comprise sodium hydroxidewith a molar ratio to the Ag salt more than 1, so that water solubilityof the solution will be increased.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows stable distribution of the Ag nanoparticles in the TEMpicture;

FIG. 2 shows the size distribution of the Ag nanoparticles in the AFMpicture.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Materials used in the preferred embodiments of the present inventioninclude:

1. Polyoxyalkylene-amine

product of Huntsman Chemical Co., Jeffamine® Amines series, including:

a. Jeffamine ED-2001:poly(oxypropylene-oxyethylene-oxypropylene)-bis-amines,polyoxyalkylene-amine with two functional groups, molecular weight=2000(a.k.a. POE-2000), white color, hydrophilic, wax-like solid, nip. 35°C., amino content=0.95 mequiv./g, average oxyethylene/oxypropyleneunit=39.5/5, structural formula:

wherein a+c=6, b=38.7;

b. Jeffamine M-2070: poly(oxypropylene-oxyethylene)-monoamine,polyoxyalkylene-amine with single functional group, molecularweight=2000 (a.k.a. POP-2000), hydrophobic, structural formula:

wherein a=10, b=31.2. Trimellitic anhydride (TMA)

product of Aldrich Chemical Co., purified with sublimation before using,structural formula:

3. Benzene tetracarboxylic dianhydride (PMDA)

product of Aldrich Chemical Co. or Sino-Japan chemical Co.

4. Poly(styrene-co-maleic anhydride) copolymers (SMA)

product of Aldrich Chemical Co. or Sino-Japan chemical Co., ratio ofstyrene/maleic anhydride or maleated polystyrene can be 1/1, 3/1, 6/1 or11/1, average molecular weight=6,000 (SMA1000), 6,000 (SMA3000), 120,000(SMA6000) and 140,000 (SMA11000).

5. 4,4′-methylenebis(phenyl isocyanate) (MDI)6. Silver nitrate

AgNO₃ (99.8%), product of Aldrich.

7. Tetrahydrofuran (THF) 8. NaBH₄

a reducing agent.

9. NaOH

In the present invention, the method for producing polymeric polyamineis to polymerize hydrophilic or hydrophobic polyoxyalkylene-amine withthe linker. The product could be hydrophilic or hydrophobic.

The reaction is exemplified with schemes. When the linker is TMA,polyoxyalkylene-amine is hydrophilic POE2000 or hydrophobic POP2000, andsodium hydroxide is added for modifying the ions after the reaction, thereaction equations are as follows:

When the linker is PMDA, polyoxyalkylene-amine is hydrophobic POP2000,and sodium hydroxide is added for modifying the ions after reaction, thereaction equations are as follows:

When the linker is SMA and polyoxyalkylene-amine is various, comb-likepolymers can be obtained as follows:

SMA Approx. ratio Approx. Mw

SMA1000 SMA3000 SMA6000 SMA11000 x/y = 1/1 x/y = 3/1 x/y = 6/1 x/y =11/1  6000  6000 12000 12000 Comb-Amphilic Approx. Mw

POP230 POP400 POP2000 POP4000 POE2000 a + c = 2~3 a + c = 5~6 a + c = 33a + c = 68 a + c = 6 b = 38.7  230  400 2000 4000 2000 SMA-M-seriesApprox. Mw

M1000 M2070 a = 3 a = 10 b = 9 b = 32 1000 2000

When the linker is MDI and polyoxyalkylene-amine is various, thereaction equations are as follows:

(Step 1)

(Step 2)

Example 1 Step (A): Preparing a Stabilizer POE2000-TMA/4COOH

First, hydrophilic POE2000 (Jeffamine® ED-2001) is purified withsublimation. THF is dewatered with calcium hydride and then preservedwith molecular sieves. Next, to a three-necked bottle (500 ml), POE2000(100 g, 0.05 mol) is added and dissolved in THF (150 ml), and thenanhydride linker TMA (19.2 g, 0.10 mol, previously dissolved in THF (50ml)) is added drop by drop, so that molar ratio of POE2000 to TMA is1:2. The reactant is mechanically stirred and filled with nitrogenduring the whole reaction. The reaction is performed at 30° C. for 2hours or longer. FT-IR spectrum is used for monitoring progress of thereaction by sampling every period of time until the anhydride functionalgroups disappear. After the reaction is completed, THF is removed bydecompression to obtain creamy glue product, amido acidPOE2000-TMA/4COOH.

Step (B): Synthesizing Ag Nanoparticles (AgNP)

To a three-necked bottle, the stabilizer POE2000/4COOH (0.069 g) isdissolved in water (50 g) which is stirred with a magnetic stirrer.AgNO₃ (0.045 g) is then added later. After 2 hours, a NaBH₄ solution(0.015 g, previously dissolved in water (50 g)) is added incontinuouslyand vigorously agitated. The solution immediately becomes black. Thereactor is filled with nitrogen during whole reaction.

Example 2 Step (A): Preparing a Stabilizer POE2000-TMA/2COOH

The product POE2000/4COOH of Example 1 is heated at 150° C. for 3 hours.Progress of the reaction is monitored with FT-IR for identifying imidofunctional groups. The product is imido acid POE2000/2COOH.

Step (B): Synthesizing Ag Nanoparticles (AgNP)

Repeat Step (B) of Example 1, but the stabilizer is replaced withPOE2000/2COOH.

Example 3 Step (A): Preparing Stabilizer POP2000-TMA/4COOH

Repeat Step (A) of Example 1, but hydrophilic POE2000 is replaced withhydrophobic POP2000 to obtain product imido acid POP2000/4COOH.

Step (B): Synthesizing Ag Nanoparticles (AgNP)

Repeat Step (B) of Example 1, but the stabilizer is replaced withPOE2000/4COOH.

Example 4 Step (A): Preparing Stabilizer POP2000-TMA/2COOH

The product POP2000/4COOH of Example 3 is heated at 150° C. for 3 hours.Progress of the reaction is monitored with FT-IR for identifying imidofunctional groups. The product is imido acid POP2000/2COOH.

Step (B): Synthesizing Ag Nanoparticles (AgNP)

Repeat Step (B) of Example 1, but the stabilizer is replaced withPOP2000/2COOH.

Example 5 Step (A): Preparing Stabilizer POP2000-PMDA/8COONa

To a three-necked bottle (500 ml), POP2000 (40 g, 0.02 mol) is added anddissolved in THF (100 ml), and then the dianhydride linker TMA (6.54 g,0.03 mol, previously dissolved in THF (100 ml)) is added drop by drop,so that molar ratio of POP2000 to PMDA is 2:3. The reactant ismechanically stirred and filled with nitrogen during the whole reaction.The reaction is performed below 30° C. for 3 hours. FT-IR spectrum isused for monitoring progress of the reaction by sampling every period oftime until the anhydride functional groups disappear. After the reactionis completed, THF is removed by decompression to obtain creamy glueproduct, amido acid POP2000-PMDA/8COOH. Into the productPOP2000-PMDA/8COOH (3.2 g, 0.08 mol), NaOH is added to form awater-soluble polymeric sodium compound.

Step (B): Synthesizing Ag Nanoparticles (AgNP)

Repeat Step (B) of Example 1, but the stabilizer is replaced withPOP2000-PMDA/8COOH.

Example 6 Step (A): Preparing Stabilizer POE2000-PMDA/4COOH

The product POE2000-PMDA/8COOH of Example 5 is heated at 150° C. for 3hours. Progress of the reaction is monitored with FT-IR for identifyingamido functional groups. The product is amido acid POE2000-PMDA/4COOH.

Step (B): Synthesizing Ag Nanoparticles (AgNP)

Repeat Step (B) of Example 1, but the stabilizer is replaced withPOE2000-PMDA/4COOH.

Example 7 Step (A): Preparing Stabilizer POP2000-SMA/COOH

SMA and POP2000 are previously dewatered in vacuum at 120° C. for 6hours. SMA3000 (10.0 g, 24.4 mmol of MA) and POP2000 (97.6 g, 48.8 mmol)are respectively dissolved in THF (50 mL) Next, SMA is incontinuouslyadded into POP2000. To prevent cross-linking, the molar ratio of POP2000to SMA is more than 1. Progress of the reaction is monitored with GPCand IR to confirm no cross-linking between the synthesized comb-likepolymers. The excess POP2000 is isolated with a solvent mixture of water(or toluene) and ethanol due to different solubilities of the comb-likepolymer and the straight-chain polyoxyalkylene-amine. The unreactedPOP2000 can be dissolved in the solvent mixture and POP2000-SMA/COOHprecipitates.

Step (B): Synthesizing Ag Nanoparticles (AgNP)

Repeat Step (B) of Example 1, but the stabilizer is replaced withPOP2000-SMA/COOH.

Example 8 Step (A): Preparing Stabilizer POE2000-POP2000-MDI

Jeffamine® ED-2001 and M2070 are first dewatered in a vacuum oven at100° C. for 6 hours, and MDI is purified with decompressingdistillation. To a three-necked bottle (100 ml), the linker MDI (1.5 g,6 mmol, previously dissolved in toluene (15 g)) is added, and thenED-2001 (5.99 g, 3 mmol, previously dissolved in toluene (10 g)) isadded drop by drop. The solution is continuously mixed with a magneticstirrer. Next, M2070 (11.99 g, 6 mmol, previously dissolved in toluene(20 g)) is added into the solution. The molar ratio of MDI:ED-2001:M2070 is 2:1:2. The reactor is filled with nitrogen during the wholereaction. Progress of the reaction is monitored with FT-IR until thecharacteristic functional groups of MDI disappear. The solvent isremoved from the solution by heating in a vacuum oven at 80° C. for 12hours. The product is creamy glue.

Step (B): Synthesizing Ag Nanoparticles (AgNP)

Repeat Step (B) of Example 1, but the stabilizer is replaced withPOE2000-POP2000-MDI.

Comparative Example 1

Repeat the procedures of Example 1, but the stabilizer POE2000-TMA/4COOHis replaced with POE2000. After the reaction, a lot of silver particlesprecipitate on the bottom of the bottle, which shows that the stabilizersynthesized by the method of the present invention is required.

Analysis of the Product

Properties and features of the product of Example 1 are analyzed withinstruments and results are as follows:

1. Formation of the Ag Nanoparticles

The Ag nanoparticles are identified by UV absorbance at wave length 400nm.

2. Stability of the Ag Nanoparticles

FIG. 1 shows TEM pictures of the products concentrated with a rotaryevaporator or a drier to have concentrations of 0.01 wt. % (picture a),0.3 wt. % (picture b), 0.01 wt. % (picture c, diluted from the slurry of0.3 wt. %), and 0.01 wt. % (picture d, diluted after evaporated). Asshown in FIG. 1, the Ag nanoparticles uniformly distribute and havediameters less than 30 nm after heating at 80° C. for 1 hour. That is,the solution containing Ag nanoparticles of the present invention ishighly stable.

3. Diameter Distribution

FIG. 2 shows AFM pictures and distribution of the Ag nanoparticles, inwhich diameters of the Ag particles range about 33˜25 nm.

Concentrating Process

The Ag nanoparticles of the present invention can be concentrated to 10wt % or higher with an evaporator or a drier, for example, decompressionat 80° C. or freezing at 0° C. The highly concentrated solution can bealso diluted and the dilution also exhibits good dispersibility andthermal stability.

The traditional silver solution has a concentration limit of 5 wt % andeasily forms participate or aggregation. Contractively, by means of thepresent invention, solid content of the solution containing Agnanoparticles can be promoted to 10 wt % or even higher. The mostimportant factor is that a novel stabilizer, polymeric polyamine, isprovided in the reduction reaction of silver salt into Ag nanoparticles.Molecular weight of the Ag nanoparticles is about 500˜10,000 mol/g, andthe functional groups may include anhydride, carboxylic acid, epoxy andisocyanate.

According to the above, features or advantages of the present inventionat least include:

1. Different sizes of Ag nanoparticles can be obtained by using asynthesized polymeric dispersant and controlling the ratio of polymericpolyamine to silver.

2. The prepared silver dispersion can be concentrated as a silver slurrywhich can be also diluted as a stable dispersion. The dispersing mediacan be water or other suitable organic solvents, for example, methanol,ethanol, IPA, acetone, ethylene glycol, dimethylformamide,N,N-dimethylacetamide N-methyl-2-pyrrolidinone, THF, MEK, etc.

3. The Ag nanoparticles of the present invention are both hydrophilicand hydrophobic and thus are compatible with polymer in nanoscale. Thehighly concentrated solution of Ag nanoparticles can be applied toblending with organic polymer (for example, PI, Epoxy, Nylon, PP, ABS,PS, etc.), so as to improve conductivity, antimicrobial (properties)thereof.

1. A method for producing a polymeric polyamine, comprising a step ofreacting the polyoxyalkylene-amine with a linker having a reactivefunctional group, wherein the polyoxyalkylene-amine has a molecularweight of 200˜10,000, and the linker is selected from the groupconsisting of anhydride, carboxylic acid, glycidyl, epoxide, isocyanate,diisocyanate, maleic anhydride and maleated polystyrene.
 2. The methodas claimed in claim 1, wherein the polyoxyalkylene-amine has astructural formula H₂N—R—NH₂, wherein R is selected from the groupconsisting of dianhydride, diacid, epoxy, diisocyanate andpoly(styrene-co-maleic anhydride) copolymers (SMA).
 3. The method asclaimed in claim 1, wherein the molar ratio of the polyoxyalkylene-amineto the linker is n:(n+1) or (n+1):1, n=1˜5.
 4. The method as claimed inclaim 1, which is performed at 25° C.˜150° C. for 1˜12 hours.
 5. Themethod as claimed in claim 1, wherein the linker is selected from thegroup consisting of benzene tetracarboxylic dianhydride (PMDA),trimellitic anhydride (TMA), adipic acid, maleic anhydride, succinicacid anhydride, phthalic anhydride,tetrahydromethyl-1,3-isobenzofurandione, dicarboxylic acid, succinicacid, p-phthalic, isophthalic acid, diglycidyl ether of bisphenol-A(DGEBA), 3,4-epoxycyclohexyl-methyl-3,4-epoxy cyclohexane carboxylate,toluene diisocyanate, methylen-biphenyldiisocyanate,1,6-cyclohexamethylene-diisocyanate, methyl isopropyl ketonediisocyanate and poly(styrene-co-maleic anhydride) copolymers (SMA). 6.The method as claimed in claim 1, wherein the linker is selected fromthe group consisting of benzene tetracarboxylic dianhydride (PMDA),trimellitic anhydride (TMA) and adipic acid.
 7. The method as claimed inclaim 1, wherein the polymeric polyamine produced is a stabilizer ordispersant of the Ag nanoparticles.